Gas-phase kinetic and mechanism study of the reactions of O3, OH, Cl and NO3 with unsaturated acetates

Abstract

Environmental contextAcetate esters, emitted into the atmosphere from both natural and anthropogenic sources, can participate in photochemical processes leading to the formation of secondary organic aerosols. We report a study on the kinetics and mechanisms of the reaction of two acetate esters with O3, OH, NO3, and Cl radicals. The results help our understanding of the chemical behaviour of this important class of compounds in the atmosphere. AbstractThe photodegradation reactions of isopropenyl acetate (IPA) and 2-methyl-2-propenyl acetate (MPA) initiated by O3, OH, Cl and NO3 radicals have been investigated in a 100 L Teflon reactor at 293 ± 3 K, by using gas chromatography with flame-ionisation detection as well as thermal desorption–gas chromatography–mass spectrometry to monitor the reactants and the products. The rate constants for the reactions of IPA and MPA with the four atmospheric oxidants were determined by using either absolute or relative rate methods. The following rate constants (in units of cm3 molecule−1 s−1) were obtained: k(O3 + IPA) = (0.37 ± 0.06) × 10−18, k(OH + IPA) = (6.44 ± 0.74) × 10−11, k(Cl+ IPA) = (4.33 ± 0.52) × 10−10, k(NO3 + IPA) = (1.62 ± 0.22) × 10−14, k(O3 + MPA) = (2.76 ± 0.40) × 10−18, k(OH + MPA) = (7.41 ± 0.92) × 10−11, k(Cl + MPA) = (3.33 ± 0.39) × 10−10, k(NO3 + MPA) = (1.34 ± 0.23) × 10−14. With the exception of the kinetic study of the reactions of O3 and OH with IPA and the mechanistic study of the reaction of IPA with O3, the current research reports the first kinetic and mechanistic investigation for these reactions at atmospheric pressure. Acetic anhydride and 1-acetoxyacetone are the main products of the reactions of IPA and MPA, respectively. On the basis of the products and estimated tropospheric lifetimes of the two esters, reaction mechanisms are proposed and the atmospheric implications are discussed.